CN107735515A

CN107735515A - Fibrous carbon and its manufacture method and electrode for nonaqueous electrolyte secondary battery mixture layer and electrode for nonaqueous electrolyte secondary battery and rechargeable nonaqueous electrolytic battery

Info

Publication number: CN107735515A
Application number: CN201680035558.0A
Authority: CN
Inventors: 小村伸弥; 平川亮太; 谷内辉; 谷内一辉; 兼松亚沙美; 大道高弘
Original assignee: Teijin Ltd
Current assignee: Teijin Ltd
Priority date: 2015-06-18
Filing date: 2016-06-16
Publication date: 2018-02-23
Also published as: JPWO2016204240A1; TWI727955B; EP3312316A1; US11532822B2; WO2016204240A1; PL3312316T3; EP3312316A4; KR20180019589A; EP3312316B1; HUE051485T2; JP6592515B2; KR102626158B1; US20180175391A1; TW201713594A

Abstract

Pass through the present invention, there is provided：Fibrous carbon, it is characterised in that average effective fiber length is 1 ~ 100 μm, and the crystal grain length (La) determined by X-ray diffraction method is 100 ~ 500nm；Electrode for nonaqueous electrolyte secondary battery mixture layer, it includes electrode active material and the carbon series conductive auxiliary agent comprising the fibrous carbon；Electrode for nonaqueous electrolyte secondary battery, it includes collector and the electrode for nonaqueous electrolyte secondary battery mixture layer being laminated on the collector；Rechargeable nonaqueous electrolytic battery, it has the electrode for nonaqueous electrolyte secondary battery.

Description

Fibrous carbon and its manufacture method and electrode for nonaqueous electrolyte secondary battery mix Nitride layer and electrode for nonaqueous electrolyte secondary battery and rechargeable nonaqueous electrolytic battery

Technical field

Formed the present invention relates to fibrous carbon, particularly carbon fiber and its manufacture method and using the fibrous carbon non- Water-Electrolyte electrode for secondary battery mixture layer and the rechargeable nonaqueous electrolytic battery electricity consumption with the electrode mixture layer Pole and the rechargeable nonaqueous electrolytic battery that there is electrode and form.

Background technology

Carbon nanomaterial, particularly avarage fiber diameter are that less than 1 μm ultrafine carbon fiber has high crystalline, highly conductive The excellent characteristic such as property, high intensity, high elastic modulus, light weight, therefore it is used as the Nano filling of high-performance composite materials.It is used Way is not limited to the enhancing Nano filling for the purpose of improving mechanical strength, also creates carbon material possessed high conductivity, Have studied as various batteries, capacitor electrode in added material, electromagnetic shielding material, anti-static material conduction Property Nano filling or the purposes as the Nano filling coordinated in the electrostatic coatings towards resin.In addition, generate conduct Chemical stability, heat endurance, the feature of fine structure of carbon material, it is desirable to the field-causing electron hair as flat-panel screens etc. Penetrate the purposes of material.Wherein, extremely expect by added to improving electric conductivity in rechargeable nonaqueous electrolytic battery.

In patent document 1, the manufacture method of the carbon fiber by following step is disclosed：(1) by including thermoplastic resin 100 mass parts and in pitch, polyacrylonitrile, poly- carbodiimide, polyimides, polybenzoxazole and aromatic polyamides The mixture of at least one kind of mass parts of thermoplasticity carbon precursor 1 ~ 150 forms the step of precursor formed body；(2) precursor formed body is applied Add stabilization processes so as to which the thermoplasticity carbon precursor in forming precursor body be stabilized and form the step for stabilizing resin combination Suddenly；(3) the step of thermoplastic resin is so as to form fibrous carbon precursor is removed by stabilisation resin combination under reduced pressure；(4) Fibrous carbon precursor is carbonized or graphited step.The carbon fiber manufactured by this method has good characteristic, but conduct Battery behavior when being used as electrode material is insufficient, it is desirable to more Large Copacity, high output.

In patent document 2, the lithium ion as negative pole receives material, and it is the carbon more than 1000 angstroms (100nm) to describe La Material.

In patent document 3, the range La for describing the bedding angle of graphite crystal is with the ratio between stacking thickness Lc (La/Lc) More than 1.5 pitch-based carbon fiber.In embodiment, the carbon fiber that Lc is 35nm or 33nm is described.The La of the carbon fiber is being counted Count in reaching 61nm, 56nm.Therefore, the carbon fiber that La is more than 100nm is still not specifically disclosed.

Prior art literature

Patent document

Patent document 1：No. 2009/125857 publication of International Publication No.

Patent document 2：Japanese Unexamined Patent Publication 10-134814 publications

Patent document 3：No. 3031197 publications of Japanese Patent No..

The content of the invention

The invention problem to be solved

It is an object of the present invention to provide the fibrous carbon that crystallinity is further improved compared with conventional carbon fiber, spy It is not carbon fiber and its manufacture method.Further, there is provided the rechargeable nonaqueous electrolytic battery electricity consumption formed using the fibrous carbon Pole mixture layer, the electrode for nonaqueous electrolyte secondary battery formed comprising the electrode mixture layer and comprising the electrode and The rechargeable nonaqueous electrolytic battery of composition.

Means for solving the problems

The present inventor etc. in view of above-mentioned prior art and be repeated further investigation result find, fibrous carbon manufacture walk In rapid, in the state of carbon precursor improve the operation of its molecularly oriented, the knot thus, it is possible to improve gained fibrous carbon Crystalline substance, so as to complete the present invention.

That is, the present invention for solving above-mentioned problem is as described below.

(1) fibrous carbon, it is characterised in that average effective fiber length is 1 ~ 100 μm, is determined by X-ray diffraction method Crystal grain length (La) is 100 ~ 500nm.

(1) fibrous carbon described in is the fibrous carbon material with defined effective fibre length, is to have high knot The fibrous carbon of crystalline substance.The fibrous carbon can be manufactured by that can improve crystalline defined manufacture method.

(2) fibrous carbon according to (1), wherein, the avarage fiber diameter of foregoing fibrous carbon is 100nm ~ 1 μm.

(2) fibrous carbon described in is the small superfine fibrous carbon of fibre diameter.

(3) fibrous carbon according to (1), wherein, the Boron contents of foregoing fibrous carbon are below 1 mass ppm.

(3) fibrous carbon described in is substantially free of boron, the i.e. fibrous carbon undoped with boron.

(4) fibrous carbon according to (1), wherein, foregoing fibrous carbon is pitch-based carbon fiber.

(4) fibrous carbon described in is the fibrous carbon using pitch as carbon precursor.

(5) electrode for nonaqueous electrolyte secondary battery mixture layer, it is included：Electrode active material and include (1) institute The carbon series conductive auxiliary agent for the fibrous carbon stated.

(5) the electrode for nonaqueous electrolyte secondary battery mixture layer described in is to comprise at least granular electrode active material (1) fibrous carbon described in and the fibre described in (1) is at least dispersed with the mutual gap of particle of the electrode active material Tie up the electrode for nonaqueous electrolyte secondary battery mixture layer of shape carbon.

(6) the electrode for nonaqueous electrolyte secondary battery mixture layer according to (5), wherein, foregoing nonaqueous electrolyte The thickness of electrode for secondary battery mixture layer is 50 ~ 5000 μm.

(6) the electrode for nonaqueous electrolyte secondary battery mixture layer described in is that the rechargeable nonaqueous electrolytic battery of thick film is used Electrode mixture layer.

(7) the electrode for nonaqueous electrolyte secondary battery mixture layer according to (5), wherein, with comprising foregoing non-aqueous Electrolyte secondary battery is by the use of the electrode of electrode mixture layer as working electrode, using lithium metal as to electrode, using comprising The LiPF of 1mol/L concentration₆Ethylene carbonate/methyl ethyl carbonate mixed solution (volume (25 DEG C) ratio=3/7), in 2.5 ~ 5V (vs.Li/Li+) determined in the range of in obtained cyclic voltammogram (CV), integrated value/oxidation current of reduction current is not shown Integrated value be less than 0.6 electrochemical reaction.

(7) the electrode for nonaqueous electrolyte secondary battery mixture layer described in is the current potential in 2.5 ~ 5V (vs.Li/Li+) In the range of the electrode for nonaqueous electrolyte secondary battery mixture layer of irreversible electrochemical reaction is not shown.

(8) the electrode for nonaqueous electrolyte secondary battery mixture layer according to (5), wherein, foregoing fibrous carbon is Meet the fibrous carbon of following conditions：With comprising being made up of the mass parts of fibrous carbon 50 and the mass parts of polyvinylidene fluoride 50 The electrode of the electrode for nonaqueous electrolyte secondary battery mixture layer of 100 mass parts as working electrode, using lithium metal as pair Electrode, use the LiPF for including 1mol/L concentration₆Ethylene carbonate/methyl ethyl carbonate mixed solution (volume (25 DEG C) ratio=3/ 7) in the cyclic voltammogram (CV) that, measure obtains in 2.5 ~ 4.4V (vs.Li/Li+) potential range, following formula (1) is met

The formulas of IA/IB ＜ 0.02 (1)

(here, IA is that oxidation current reaches when cyclic voltammogram measure is carried out in 2.5 ~ 4.4V (vs.Li/Li+) potential range Maximum among current value during maximum, IB are that circulation volt is carried out in 2.5 ~ 5V (vs.Li/Li+) potential range The current value under 5V when Antu determines).

(8) the electrode for nonaqueous electrolyte secondary battery mixture layer described in is the electricity in 2.5 ~ 4.4V (vs.Li/Li+) The electrode for nonaqueous electrolyte secondary battery mixture layer comprising fibrous carbon of electrochemical reaction is not shown in the range of position.

(9) electrode for nonaqueous electrolyte secondary battery, it includes collector and (5) institute being laminated on foregoing collector The electrode for nonaqueous electrolyte secondary battery mixture layer stated.

(9) electrode for nonaqueous electrolyte secondary battery described in is comprising collector and at least one of the collector Be laminated on surface and integration (5) described in electrode mixture layer electrode for nonaqueous electrolyte secondary battery.

(10) rechargeable nonaqueous electrolytic battery, it has the electrode for nonaqueous electrolyte secondary battery described in (9).

(10) rechargeable nonaqueous electrolytic battery described in is that negative or positive electrode or positive pole and negative pole are electricity described in (9) The rechargeable nonaqueous electrolytic battery of pole.

(11) manufacture method of fibrous carbon, it is the method comprising following step：

(1) fibrosis step, comprising thermoplastic resin and will be 1 ~ 150 mass relative to the mass parts of aforementioned thermoplastic resin 100 The resin combination of the mesophase pitch of part is molded in the molten state, and foregoing mesophase pitch thus is carried out into fibrosis and obtained To resin compounded fiber；

(2) stabilization step, aforementioned resin composite fibre is stabilized, obtains resin compounded and stabilize fiber,

(3) thermoplastic resin removal step, stabilized from foregoing resin compounded in fiber and remove aforementioned thermoplastic resin, so as to To stabilisation fiber；

(4) be carbonized calcining step, and foregoing stabilisation fiber is heated under not active atmosphere so as to be carbonized or graphitization, obtains fibre Tie up shape carbon；

Characterized in that, the tropism control that foregoing fibrosis step has mesophase pitch operates.

(11) manufacture method of the fibrous carbon described in is in the fibrosis step of (1), will include thermoplastic resin When carrying out spinning or film forming in the molten state with the resin combination of the island structure of mesophase pitch, there is control interphase The manufacture method of the operation of the molecularly oriented of pitch.That is, it is included in being improved while resin combination spinning or film forming Between asphalt phase molecularly oriented fibrosis step.

(12) manufacture method of the fibrous carbon according to (11), wherein,

Foregoing tropism control operation includes applying the method for deformation by shearing or applied by stretching in the method for deformation extremely Few one.

(12) manufacture method described in is that tropism control operation passes through the shearing or stretching at spinning head bore or rectangle head bore And the manufacture method carried out.

(13) manufacture method of the fibrous carbon according to (11), wherein,

Mentioned by shearing apply deformation method and mentioned by stretching apply deformation method in shearing deformation speed and Tensile deformation speed is respectively 5 ~ 10000s^-1。

(13) manufacture method described in be by shearing deformation speed and tensile deformation speed control in defined scope Manufacture method.

(14) manufacture method of the fibrous carbon according to (11), wherein,

Method mentioned by stretching application deformation is the stretching in the downstream side of head bore.

(14) manufacture method described in is sprayed by stretching from the spinneret orifice or slit of spinning head bore or rectangle head bore Resin combination is so as to by the Mesophase Pitch Fiberss in resin combination while improving the molecularly oriented of mesophase pitch Manufacture method.

The effect of invention

According to the present invention it is possible to obtain the threadiness that crystallinity is improved compared with the carbon material obtained by prior art Carbon, battery material can be suitably used as.In addition, the fibrous carbon of the present invention in addition to battery material, is used as enhancing Nano filling, capacitor electrode in added material, electromagnetic shielding material, the conductive nanometer of anti-static material fill out The purposes of the field electron emission materials of material, the Nano filling coordinated in the electrostatic coatings towards resin, flat-panel screens etc. In and it is promising.

Brief description of the drawings

Fig. 1 is the sectional view of the internal structure for the ejiction opening part for showing spinning head bore.

Fig. 2 is the cyclic voltammogram using electrode measure in 2.5 ~ 5V (vs.Li/Li+) potential range of embodiment 1 (CV curves).

Fig. 3 is the cyclic voltammetric using electrode measure in 2.5 ~ 4.4V (vs.Li/Li+) potential range of embodiment 1 Scheme (CV curves).

Fig. 4 is the discharge and recharge measurement result of the battery in embodiment 1.

Fig. 5 is the electron micrograph (2000 times) of the superfine fibre shape carbon of embodiment 2.

Fig. 6 is the figure of the density-powder specific insulation for the superfine fibre shape carbon for showing embodiment 2 and embodiment 3.

Fig. 7 is the electron micrograph (2000 times) of the superfine fibre shape carbon of embodiment 3.

Fig. 8 is the cyclic voltammogram using electrode measure in 2.5 ~ 5V (vs.Li/Li+) potential range of comparative example 1 (CV curves).

Fig. 9 is the cyclic voltammetric using electrode measure in 2.5 ~ 4.4V (vs.Li/Li+) potential range of comparative example 1 Scheme (CV curves).

Figure 10 is the discharge and recharge measurement result of the battery in comparative example 1.

Figure 11 is the cyclic voltammetric using electrode measure in 2.5 ~ 5V (vs.Li/Li+) potential range of comparative example 2 Scheme (CV curves).

Figure 12 is lied prostrate using the circulation of electrode measure in 2.5 ~ 4.4V (vs.Li/Li+) potential range of comparative example 2 Antu (CV curves).

Figure 13 is the discharge and recharge measurement result of the battery in comparative example 2.

Figure 14 is the cyclic voltammetric using electrode measure in 2.5 ~ 5V (vs.Li/Li+) potential range of comparative example 3 Scheme (CV curves).

Figure 15 is lied prostrate using the circulation of electrode measure in 2.5 ~ 4.4V (vs.Li/Li+) potential range of comparative example 3 Antu (CV curves).

Figure 16 is the discharge and recharge measurement result of the battery in comparative example 3.

Figure 17 is the electron micrograph (2000 times) of the fibrous carbon precursor of embodiment 4.

Figure 18 is the reference chart for exporting to obtain with black and white two-value by Fig. 5 electron micrograph.

Figure 19 is the reference chart for exporting to obtain with black and white two-value by Fig. 7 electron micrograph.

Figure 20 is the reference chart for exporting to obtain with black and white two-value by Figure 17 electron micrograph.

Embodiment

Hereinafter, the present invention will be described for pin.

1. fibrous carbon

The character of 1-1. fibrous carbons

The present invention fibrous carbon be substantially made up of carbon, for example, graphite, graphene, CNT, carbon nanohorn, Fullerene, carbon black, activated carbon, carbon fiber.The fibrous carbon of the present invention is characterised by its crystallinity.As crystalline index The crystal grain length (La) determined by X-ray diffraction method for 100 ~ 500nm, be preferably 110 ~ 500nm, more preferably 130 ~ 500nm.During less than 100nm, the electric conductivity of fibrous carbon is insufficient.On the other hand, crystallite dimension is surveyed by X-ray diffraction method Fixed, but if crystal growth is excessive, then evaluated error becomes big, and substantial 500nm is test limit.

In the present invention, the crystal grain length (La) determined by X-ray diffraction method refers to by Japanese Industrial Standards JIS R The value of 7651 (2007 annual versions) " lattice constant and Crystal size determination method of carbon material " and measure.

The fibrous carbon of the present invention has high conductivity preferably in the state of packed density is low.The reason for this is that filling out Electric conductivity can be assigned with lower addition concentration by filling the fibrous carbon with high conductivity under low density state.It is specific and Speech, with packed density 0.4g/cm³Powder volume resistance during filling is preferably below 1 Ω cm, is more preferably 0.5 Ω cm Below.During more than 1 Ω cm, the addition quantitative change of the fibrous carbon needed to improve electric conductivity is more, and it is not preferable.Lower limit It is not particularly limited, it is however generally that for 0.0001 Ω cm or so.

The present invention fibrous carbon from formed electrode mixture layer in conductive network ability, improve battery output, From the viewpoint of cell durability is improved, preferably carbon fiber.As carbon fiber, in addition to CNT, carbon nanobelts etc. Vapor phase growth carbon material.Due to needing for the high carbon material of crystallinity, the more preferably pitch-based carbon fiber compared with PAN systems.

The interplanar distance (d002) determined by X-ray diffraction method of the fibrous carbon of the present invention is preferably 0.335 ~ 0.340nm, more preferably 0.335 ~ 0.339nm.By the scope for 0.335 ~ 0.340nm, graphite crystallization is high, oxidative resistance It is excellent.

The thickness (Lc) of the graphene (network plane group) of the fibrous carbon of the present invention is preferably 1.0 ~ 130nm.Less than 1.0nm When, the electrical conductivity of carbon material significantly reduces, and it is not preferable.Lc lower limit is more preferably more than 5nm, more preferably 10nm Above, more preferably more than 30nm, particularly preferably more than 50nm.Lc higher limit is preferably below 150nm, more preferably Below 130nm, particularly preferably below 100nm.

The avarage fiber diameter of the fibrous carbon of the present invention is preferably 10 ~ 1000nm.The higher limit of avarage fiber diameter is excellent Elect as below 900nm, more preferably below 800nm, more preferably below 700nm, still more preferably for 600nm with Under, particularly preferably below 550nm, be most preferably below 500nm.The lower limit of avarage fiber diameter be preferably more than 50nm, More preferably more than 100nm, more preferably more than 150nm.

If being less than 10nm, heap density is very small, and operability is poor.In addition, when forming electrode mixture layer, electrode be present The tendency of intensity decreases.During more than 1000nm, gap is also easy to produce in electrode mixture layer content, it is close to be difficult to raising electrode sometimes Degree.

Here, the fibre diameter in the present invention refers to use by field emission type SEM with 2,000 times Multiplying power shoots the value of obtained photo measure.

The average effective fiber length of fibrous carbon is preferably 1 ~ 100 μm, more preferably 1 ~ 50 μm, more preferably 5 ~ 20μm.During less than 1 μm, electric conductivity, the intensity of electrode and electrolyte in electrode mixture layer are protected fluidity and reduced, and it is not preferable. During more than 100 μm, the dispersiveness of fibrous carbon is damaged, and it is not preferable.That is, when fibrous carbon is long, fibrous carbon becomes easy It is orientated in the face of electrode mixture layer on direction (direction parallel with the surface of electrode mixture layer).That is, fiber is hindered Shape carbon is orientated on the film thickness direction (direction vertical with the surface of electrode mixture layer) of electrode mixture layer, as a result, It is difficult to form conductive path on the film thickness direction of electrode mixture layer.

In the present invention, the length of fiber is not actual fibre length, but is defined by effective fibre length.It is managed By being, fibrous carbon may not contribute to conduction in electrode mixture layer with the fibre length of reality.For example, mixed in electrode Fiber can be bent or agglomerating in compound layer, therefore not contribute to conduction with the fibre length of reality sometimes.In the present invention, The effective fibre length of fibrous carbon is defined as connecting the length of the most long line segment at both ends in the fibrous carbon of monomer.Change Yan Zhi, it is that the fibrous carbon of monomer is capable of the maximum air line distance of conduction.That is, fibrous carbon has complete linear structure When, effective fibre length and its fibre length are roughly equal.When fibrous carbon has a branched structure, when agglomerating, refer to connection position The length of maximum line segment between 2 points on the fibrous carbon of the monomer.

The ratio between the average effective fiber length (L) and avarage fiber diameter (D) of the fibrous carbon of the present invention (L/D) is preferably More than 30, more than 40 are more preferably.It is more than 30 by making than (L/D), can be efficiently formed and lead in electrode mixture layer Electric pathway, it is possible to increase the cycle characteristics of gained battery.When being less than 30 than (L/D), the shape of conductive path in electrode mixture layer Into easily becoming insufficient, the resistance value of the film thickness direction of electrode mixture layer will not be reduced fully sometimes.Than the upper limit of (L/D) Value is not particularly limited, it is however generally that for less than 10000, preferably less than 5000, more preferably less than 1000.More than 10000 When, the dispersiveness of fibrous carbon is damaged, and it is not preferable.

The fibrous carbon of the present invention is not particularly limited, and is preferably the linear structure for not having branch substantially.Branch is The main shaft for referring to fibrous carbon has dendritic countershaft in the main shaft of branched part way, fibrous carbon.It is substantially straight without branch Cable architecture refers to the degree of branching of fibrous carbon for below 0.01/μm.

It should illustrate, the fibrous carbon is in the form of on the whole having threadiness, in addition to for example multiple fibers Shape carbon contact or with reference to and be provided integrally with fiber shape material (such as Spherical Carbon connect into beading obtained from material, Extremely short at least 1 or plurality of fibers combine obtained material by welding etc.).

The present invention fibrous carbon metallic element containing ratio amount to be preferably below 50ppm, more preferably 30ppm with Under, more preferably below 20ppm.When metal containing ratio is more than 50ppm, easily make battery because of the catalyst action of metal Deterioration.In the present invention, the containing ratio of metallic element refers to Li, Na, Ti, Mn, Fe, Ni and Co total containing ratio.Especially, Fe Containing ratio be preferably below 5ppm, more preferably below 3ppm, more preferably below 1ppm.Fe containing ratio is more than During 5ppm, it is particularly easy to make deterioration of battery, it is not preferable.

Hydrogen, nitrogen, ash content in the fiber of the fibrous carbon of the present invention are both preferably below 0.5 mass %, are more preferably 0.3 Below quality %.When hydrogen, nitrogen, ash content in fibrous carbon are below 0.5 mass %, the faults of construction of graphite linings further by Suppress, the side reaction in battery can be suppressed, so it is preferred that.

The fibrous carbon of the present invention is preferably substantially free of boron.Exist and carbon atom bonding on the surface of fibrous carbon During boron atom, the boron atom turns into active site and is possible to trigger the decomposition reaction of cell electrolyte.Here, being substantially free of is Finger Boron contents are below 1 mass ppm.

The fibrous carbon of the present invention is preferably the fibrous carbon for meeting following conditions：With comprising by the mass of fibrous carbon 50 The electricity of the electrode for nonaqueous electrolyte secondary battery mixture layer of 100 mass parts of part and the mass parts of polyvinylidene fluoride 50 composition Pole, using lithium metal as to electrode, uses the LiPF for including 1mol/L concentration as working electrode₆Ethylene carbonate/carbonic acid Methyl ethyl ester mixed solution (volume (25 DEG C) ratio=3/7), measure obtains in 2.5 ~ 4.4V (vs.Li/Li+) potential range In cyclic voltammogram (CV), meet following formula (1)

The formulas of IA/IB ＜ 0.02 (1)

That is, preferably electrochemistry is not shown in 2.5 ~ 4.4V (vs.Li/Li+) potential range in fibrous carbon of the invention Reaction.Here, " electrochemical reaction is not shown " refers to comprising by the mass parts of fibrous carbon 50 and polyvinylidene fluoride (strain formula Commercial firm's Network レ Ha systems, W#7200) 50 mass parts composition 100 mass parts electrode mixture layer electrode as working electrode, Using lithium metal as to electrode, the LiPF for including 1mol/L concentration is used₆Ethylene carbonate/methyl ethyl carbonate mixed solution (volume (25 DEG C) ratio=3/7, キシダ chemical companies system) is used as solvent, in 2.5 ~ 4.4V (vs.Li/Li+) potential range Determine in obtained cyclic voltammogram (CV), without substantial peak.Here, " not having substantial peak " refers in satisfaction State formula (1).

By using the fibrous carbon that electrochemical reaction is not shown in 2.5 ~ 4.4V (vs.Li/Li+) potential range, The non-water power of the side reactions such as the reaction of decomposition, conductive auxiliary agent and electrolyte for being difficult to that electrolyte occurs under high voltages can be provided Solve electrolitc secondary cell.

The manufacture method of 1-2. fibrous carbons

For the fibrous carbon as the present invention, preferable form, the i.e. manufacture method of pitch-based carbon fiber state It is bright.The present invention pitch-based carbon fiber manufacture method can for example by hereafter record (1) ~ (4) the step of and manufacture.

(1) fibrosis step, comprising thermoplastic resin and will be 1 ~ 150 matter relative to the mass parts of thermoplastic resin 100 The resin combination of mesophase pitch for measuring part is molded in the molten state, foregoing mesophase pitch is thus subjected to fibrosis and Resin compounded fiber is obtained, the step has the tropism control operation for the molecularly oriented for improving foregoing mesophase pitch；

(4) be carbonized calcining step, and foregoing stabilisation fiber is heated under not active atmosphere so as to be carbonized or graphitization, obtains pole Fine carbon.

＜ thermoplastic resins ＞

The thermoplastic resin used in the manufacture method of the pitch-based carbon fiber of the present invention is required to manufacture resin compounded fiber, Need to be easily moved away in thermoplastic resin removal step simultaneously.As such thermoplastic resin, can exemplify poly- It is the polyacrylate such as alkene, polymethacrylates, polymethyl methacrylate based polymer, polystyrene, makrolon, poly- Aromatic ester, polyester, polyamide, polyestercarbonate, polysulfones, polyimides, PEI, polyketone, PLA.It is excellent among these Choosing uses polyolefin.

As the concrete example of polyolefin, can enumerate polyethylene, polypropylene, poly- 4- methylpentenes -1 and comprising these Copolymer.From the viewpoint of being easily removed from thermoplastic resin removal step, preferably using polyethylene.As polyethylene, The low-density such as high-pressure process low-density polyethylene, vapor phase method solwution method high-pressure process straight-chain low density polyethylene (LDPE) can be enumerated to gather The homopolymers such as ethene, medium density polyethylene and high density polyethylene (HDPE)；The copolymer of ethene and alpha-olefin, ethylene vinyl acetate The ethene such as ester copolymer and the copolymer of other vinyl monomers.

The melt mass flow according to JIS K 7210 (1999 year) measure of the thermoplastic resin used in the present invention Speed (MFR) is preferably 0.1 ~ 10g/10 minutes, more preferably 0.1 ~ 5g/10 minutes, particularly preferably 0.1 ~ 3g/10 minutes. If MFR is above range, can making mesophase pitch, differential dissipates well in thermoplastic resin.In addition, moulding resin During composite fibre, by stretching fiber, it can further reduce the fibre diameter of gained carbon fiber.The thermoplastic used in the present invention Property resin from can with from the viewpoint of mesophase pitch easily melting mixing, in the case of amorphism, glass transition Temperature is preferably less than 250 DEG C, and in the case of crystallinity, fusing point is preferably less than 300 DEG C.

＜ mesophase pitch ＞

Mesophase pitch refers to the pitch that can form optical anisotropy phase (liquid crystalline phase) in the molten state.As the present invention The middle mesophase pitch used, can enumerate using coal, oil bottoms as raw material pitch, using the aromatic hydrocarbons such as naphthalene as The pitch of raw material.For example, the mesophase pitch from coal can be used as main body by the hydrogenation heat treatment using coal tar asphalt Processing, using hydrogenation heat treatment solvent extraction obtained as processing of main body etc..

More specifically, can be obtained by following methods.

First, by the coal tar asphalt that the softening point for eliminating composition insoluble in quinoline is 80 DEG C in the catalysis of Ni-Mo systems It is hydrogenated with the presence of agent, under conditions of pressure 13MPa, 340 DEG C of temperature, obtains hydrogenation of coal tar pitch.By the hydrogenation coal tar Oil asphalt at ambient pressure, be heat-treated at 480 DEG C after, decompression remove low boiling point component, obtain thick mesophase pitch.This is thick Mesophase pitch is filtered so as to remove foreign matter at a temperature of 340 DEG C using filter, it is hereby achieved that among refined Asphalt phase.

The optical anisotropy content (middle one after another) of mesophase pitch is preferably more than 80%, more preferably more than 90%.

In addition, the softening point of above-mentioned mesophase pitch is preferably 100 ~ 400 DEG C, more preferably 150 ~ 350 DEG C.

＜ resin combinations ＞

The resin group comprising thermoplastic resin and mesophase pitch used in the manufacture method of the pitch-based carbon fiber of the present invention Compound (hereinafter also referred to mesophase pitch composition) preferably comprises thermoplastic resin and relative to the matter of thermoplastic resin 100 Measure the mesophase pitch that part is 1 ~ 150 mass parts.The content of mesophase pitch is more preferably 5 ~ 100 mass parts.If interphase The content of pitch is more than 150 mass parts, then can not obtain with the resin compounded fiber for it is expected fibre diameter, if being less than 1 matter Part is measured, then produces the problems such as can not being manufactured inexpensively target carbon fiber, it is not preferable.

In order to manufacture the carbon fiber that fibre diameter is below 1000nm, mesophase pitch in thermoplastic resin it is scattered straight Footpath is preferably 0.01 ~ 50 μm, more preferably 0.01 ~ 30 μm.If the dispersion diameter of the mesophase pitch in thermoplastic resin is inclined Scope from 0.01 ~ 50 μm, then it is difficult to manufacture desired carbon fiber sometimes.It should illustrate, it is middle in mesophase pitch composition Asphalt phase forms spherical or elliptoid island phase, and the dispersion diameter in the present invention is on island mutually to refer to that its is straight in the case of spherical Footpath, refer to its long axial length in the case of being mutually ellipticity on island.

Above-mentioned 0.01 ~ 50 μm of dispersion diameter is preferably after mesophase pitch composition is kept for 3 minutes at 300 DEG C Maintain above range, more preferably kept for 5 minutes at 300 DEG C after also maintain above range, particularly preferably at 300 DEG C keep 10 Above range is also maintained after minute.If in general, mesophase pitch composition is kept in the molten state in advance, In resin combination, mesophase pitch aggegation over time.If mesophase pitch aggegation is more than 50 μ so as to its dispersion diameter M, then it is difficult to manufacture desired carbon fiber sometimes.The aggegation speed of mesophase pitch in resin combination is hot used in The species of plastic resin and mesophase pitch and change.

Mesophase pitch composition can be by the way that thermoplastic resin and mesophase pitch be kneaded to make in the molten state Make.The melting mixing of thermoplastic resin and mesophase pitch can be carried out using known device.It is, for example, possible to use it is selected from More than a kind in single-screw kneading machine, double-screw type kneading machine, mixing mill, Banbury mixer.Among these, from making Between asphalt phase microdispersed purpose is set out well in thermoplastic resin, preferably using double-screw type kneading machine, particularly preferably The double-screw type kneading machine rotated using each axle towards equidirectional.

As melting temperature, then it is not particularly limited as long as thermoplastic resin and mesophase pitch are molten condition, preferably For 100 ~ 400 DEG C, preferably 150 ~ 350 DEG C.If melting temperature is less than 100 DEG C, mesophase pitch can not form molten State, it is difficult to dissipate its differential in thermoplastic resin.When on the other hand, more than 400 DEG C, thermoplastic resin or centre are carried out sometimes The decomposition of asphalt phase.In addition, the time as melting mixing, preferably 0.5 ~ 20 minute, more preferably 1 ~ 15 minute.Melting is mixed When the time of refining is less than 0.5 minute, micro- difficulties in dispersion of the mesophase pitch in thermoplastic resin.On the other hand, more than 20 points Zhong Shi, the productivity ratio of carbon fiber significantly reduce.

Melting mixing is preferably carried out under not active atmosphere of the oxygen content less than 10 volume %, more preferably in oxygen content Carry out under not active atmosphere less than 5 volume %, particularly preferably carried out under not active atmosphere of the oxygen content less than 1% volume. The mesophase pitch used in the present invention is hindered in thermoplastic sometimes by being reacted in melting mixing with oxygen to be modified Differential in property resin dissipates.Therefore, in order to suppress the reaction of oxygen and mesophase pitch, preferably melted under not active atmosphere Melt mixing.

＜ resin compounded fibers ＞

As the method that resin compounded fiber is manufactured by above-mentioned mesophase pitch composition, as long as desired carbon fiber can be made Do not limit then, can exemplify using spinning head bore by the method for mesophase pitch composition melt spinning, using rectangular head Hole is by the method for mesophase pitch composition melted masking.

In order to obtain the carbon fiber of the present invention, in the stage for obtaining resin compounded fiber, improve in resin compounded fiber Comprising mesophase pitch molecularly oriented tropism control operation be necessary.It is molten in order to improve in tropism control operation Melt the molecularly oriented of the mesophase pitch of state, it is necessary to deform the mesophase pitch of molten condition.As such orientation Control operation, it can exemplify and apply the method for deformation by shearing to the mesophase pitch of molten condition, applied by stretching The method of deformation.These methods can only carry out one, and both can also be applied in combination.Especially, deformation is applied by stretching Method improve molecularly oriented effect it is big, so it is preferred that.

As by shear apply deformation method, can enumerate increase molten condition mesophase pitch composition line The method of speed.Specifically, in the stream of spinning head bore or rectangle head bore, by the mesophase pitch for improving molten condition Composition by speed, can pass through to shear and apply deformation.

As the method for applying deformation by stretching, the line of the mesophase pitch composition for molten condition of sening as an envoy to can be illustrated The method that the ejection side of speed towards spinning head bore or rectangle head bore gradually increases.Specifically, can enumerate makes the stream of head bore The sectional area on road towards spray method (deformation inside head bore) that side is gradually reduced, by from spinning head bore or rectangle head bore Method (change head bore outside of the mesophase pitch composition that squit hole sprays to be drawn more than the linear velocity for spraying linear velocity Shape) etc..In the case of the deformation inside head bore, the mesophase pitch of molecularly oriented is improved easily because of heat by deformation Relaxation and cause molecularly oriented reduction.On the other hand, in the case of the deformation outside head bore, improved point by deformation The mesophase pitch of sub- orientation is cooled at once and mobility reduces, and thus maintaining the molecularly oriented of mesophase pitch. Therefore, operated as tropism control, apply the method for deformation by stretching preferably outside head bore.

These methods are it is important that control shearing deformation speed, tensile deformation speed.

Shearing deformation speed and tensile deformation speed are respectively 5 ~ 10000s^-1, be preferably 100 to 1400s^-1.Less than 5s^-1 When, it can not fully improve the molecularly oriented of mesophase pitch.More than 10000s^-1When, the deformation of mesophase pitch can not be followed, Threadiness can not be morphed into.

Deformation starting point to the distance of deformation end point inside the head bore of spinning head bore or rectangle head bore is preferably 0.1 ~5mm.The lower limit of distance is preferably 0.3mm, more preferably 0.5mm, more preferably 0.7mm, particularly preferably 1.0mm. The higher limit of distance is preferably 4.0mm, more preferably 3.0mm, is most preferably 2.0mm.Here, the deformation inside head bore starts Point to the distance of deformation end point refers in the side along the axis parallel with slit stream for the necking section that head bore is internally formed To length.Fig. 1 is the sectional view of the internal structure for the ejiction opening part for showing spinning head bore.In Fig. 1,10 be spinning head bore, 15 be slit stream.11 be that the flowing path section of spinning head bore starts reduced position, for the deformation starting point in the present invention.13 are The position that the reduction of the flowing path section of spinning head bore terminates, for the deformation end point in the present invention.Deformation starting point to deform knot The distance of spot is connection deformation starting point 11 and the direction along the axis parallel with slit stream for deforming end point 13 Air line distance.The importing angle θ formed in the necking section of spinning head bore is 30 ~ 90 degree, is preferably 40 ~ 80 degree, is more preferably 45 ~ 75 Degree.

In the case of spinning head bore using above-mentioned shape, the mesophase pitch composition of molten condition passes through spinning head bore Stream in when, by shearing and appropriateness apply deformation, it is possible to increase the molecularly oriented of mesophase pitch.

Deformation starting point to the distance of deformation end point outside the head bore of spinning head bore is preferably 5 ~ 100mm.Distance Lower limit be preferably 6mm, more preferably 7mm, particularly preferably 8mm.The higher limit of distance is preferably 90mm, is more preferably 80mm, more preferably 70mm, particularly preferably 60mm, it is most preferably 50mm.Here, the deformation starting point outside head bore Distance to deformation end point refers to beeline from the front end of the slit flowing path outlet of spinning head bore to casting area, and use is cold But during roller, refer to the beeline in the mobile face of chilling roll.

Controlled like that by above-mentioned, it is possible to increase the molecularly oriented of mesophase pitch, while fibre diameter can be obtained The small carbon fiber of the coefficient of variation.

Temperature when improving the operation of the molecularly oriented of mesophase pitch needs the melting temperature higher than mesophase pitch, Preferably 150 ~ 400 DEG C, more preferably 180 ~ 350 DEG C.During more than 400 DEG C, the deformation rate transition of mesophase pitch becomes big, difficult In the form of keeping fiber.

It is preferably 2 ~ 100, more preferably 2 ~ 50 to spray linear velocity and the ratio of hauling speed, i.e. draw ratio.If greater than 100, then the deformation of mesophase pitch can not be followed, threadiness can not be morphed into, it is not preferable.If, can not less than 2 The molecularly oriented of mesophase pitch is improved, as a result, the crystallinity step-down of gained fibrous carbon.

In addition, the fibrosis step of resin compounded fiber can have cooling step.As cooling step, for example, molten In the case of melting spinning, can enumerate cooling spinning head bore dirty atmosphere method., can be with the case of melted masking Enumerate the method in the dirty setting chilling roll of rectangle head bore.By setting cooling step, can adjust mesophase pitch because The region for stretching and deforming, the speed of deformation can be adjusted.In addition, by setting cooling step, make the tree after spinning or film Fat composite fibre cools and solidifies at once, so as to stably be molded.

＜ resin compoundeds stabilize fiber ＞

For by it is above-mentioned like that in a manner of obtained resin compounded fiber, the mesophase pitch included in the resin compounded fiber is fine Dimension stabilizes (also referred to as non-fusible) and stabilizes fiber so as to make resin compounded.Stabilize can by using air, oxygen, The gas flow of ozone, nitrogen dioxide, halogen etc. is handled, entered using method known to solution processing of acidic aqueous solution etc. etc. OK.From productivity ratio aspect, it is non-fusible that progress is preferably handled by gas flow.

As used gas componant, from the viewpoint of processing easiness, preferably air, oxygen or it is included Mixed gas, from the relation of cost, particularly preferably using air.As used oxygen concentration, it is preferably in 10 ~ 100 volume % of all gas composition scope.If oxygen concentration is less than 10 volume % of all gas composition, for The stabilisation of the mesophase pitch included in resin compounded fiber needs the plenty of time.

Stabilized reaction temperature is preferably 50 ~ 350 DEG C, more preferably 60 ~ 300 DEG C, is more preferably 100 ~ 300 DEG C, particularly preferably 200 ~ 300 DEG C.Stabilized processing time is preferably 10 ~ 1200 minutes, more preferably 10 ~ 600 minutes, More preferably 30 ~ 300 minutes, particularly preferably 60 ~ 210 minutes.

Handled by aforementioned stable, the softening point of mesophase pitch significantly rises.From obtaining the mesh of desired carbon fiber Set out, the softening point of mesophase pitch is preferably more than 400 DEG C, more preferably more than 500 DEG C.

＜ thermoplastic resin removal steps ＞

Then, fiber, the thermoplastic resin that will wherein include are stabilized for the resin compounded obtained in a manner of as described above Remove so as to separate stabilisation fiber.In the step, while suppressing to stabilize the thermal decomposition of fiber, decompose and remove thermoplastic Property resin.As the method for decomposing removal thermoplastic resin, for example, the side that thermoplastic resin is removed using solvent The method that method, thermal decomposition remove thermoplastic resin.

The thermal decomposition of thermoplastic resin is preferably carried out under not active gases atmosphere.Alleged not active gases atmosphere herein Refer to the atmospheres such as carbon dioxide, nitrogen, argon gas, its oxygen concentration is preferably below 30 volume ppm, is more preferably 20 volumes Below ppm.As the not active gases used in this step, from the relation of cost, preferably using carbon dioxide and nitrogen, Particularly preferably use nitrogen.

The thermal decomposition of thermoplastic resin can also be carried out under reduced pressure.By thermally decomposing under reduced pressure, can fully remove Thermoplastic resin.As a result, carbon fiber or graphitized fibre can subtract obtained from stabilizing fibers carbonization or graphitization Few interfibrous welding.Atmosphere pressure is more low more preferred, preferably below 50kPa, is more preferably below 30kPa, is further excellent Elect below 10kPa, particularly preferably below 5kPa as.On the other hand, it is difficult to reach complete vacuum, therefore the lower limit of pressure leads to Often it is more than 0.01kPa.

When carrying out the thermal decomposition of thermoplastic resin under reduced pressure, as long as keeping above-mentioned atmosphere pressure, then there may be micro Oxygen, not active gases.Especially, if there is micro not active gases, then inhibit hot bad because of thermoplastic resin Interfibrous welding caused by change, so it is preferred that.It should illustrate, alleged micro oxygen refers to that oxygen concentration is 30 herein Below volume ppm, micro not active gases refer to that activity gas concentration is not below 20 volume ppm.It is used not active The species of gas is as described above.

The temperature of thermal decomposition is preferably 350 ~ 600 DEG C, more preferably 380 ~ 550 DEG C.The temperature of thermal decomposition is less than 350 DEG C When, although can suppress to stabilize the thermal decomposition of fiber, the thermal decomposition of thermoplastic resin sometimes can not be carried out fully.The opposing party Face, during more than 600 DEG C, although the thermal decomposition of thermoplastic resin is fully carried out, all it is thermal decomposited sometimes up to fiber is stabilized, The result is that yield is easily reduced.As the time of thermal decomposition, preferably 0.1 ~ 10 hour, more preferably 0.5 ~ 10 hour.

In the manufacture method of the present invention, stabilization step and thermoplastic resin removal step preferably by resin compounded fiber or Resin compounded stabilizes fiber with 2kg/m²Weight per unit area below be maintained on supporting substrate and carry out.By being maintained at On supporting substrate, can suppress during because of stabilization processes or heating when thermoplastic resin removes and caused by resin compounded Fiber or resin compounded stabilize the aggegation of fiber, can keep aeration.

Material as supporting substrate is not, it is necessary to deform, corrode because of solvent, heating.In addition, as supporting substrate Heat resisting temperature, from need under the heat decomposition temperature of above-mentioned thermoplastic resin removal step it is indeformable from the viewpoint of, preferably With more than 600 DEG C heat resistances.As such material, stainless steel and other metal materials, aluminum oxide, silica can be enumerated Deng ceramic material.

In addition, the shape as supporting substrate, preferably has the shape of aeration in a direction orthogonal to the surface.Make For such shape, preferably eyed structure.The sieve aperture of mesh is preferably 0.1 ~ 5mm.When sieve aperture is more than 5mm, fiber it is easy because Heat and aggegation on the line of mesh, the stabilisation of mesophase pitch, the removal of thermoplastic resin sometimes becomes insufficient. On the other hand, when the sieve aperture of mesh is less than 0.1mm, because the percent opening of supporting substrate reduces, the ventilation of supporting substrate sometimes is caused Property reduce.

＜ carbonization calcining steps ＞

By the way that aforementioned stable chemical fibre is tieed up into carbonization and/or graphitization under not active atmosphere, the carbon fiber of the present invention can be obtained. Container as the container now used, preferably the crucible shape of graphite.Here, carbonization refers in lower temperature (preferably 1000 DEG C or so) under heat, graphitization refers to by heating (be preferably 3000 DEG C or so) at a higher temperature so that graphite Crystal growth.

The not active gases used when the carbonization tieed up as aforementioned stable chemical fibre and/or graphitization, can enumerate nitrogen, argon Gas etc..Oxygen concentration in not active atmosphere is preferably below 20 volume ppm, is more preferably below 10 volume ppm.Carbonization and/ Or heating-up temperature during graphitization is preferably 500 ~ 3500 DEG C, more preferably 800 ~ 3200 DEG C.During particularly as graphitization Temperature, preferably 2000 ~ 3200 DEG C, more preferably 2100 ~ 3000 DEG C.When temperature during graphitization is less than 2000 DEG C, hamper Crystal growth, crystal grain length become insufficient, and electric conductivity significantly reduces sometimes.In addition, when graphitization temperature is more than 3000 DEG C, from It is preferable from the point of view of crystal growth viewpoint, but the tendency of the oxygen content reduction of carbon fiber is present.Calcination time is preferably 0.1 ~ 24 Hour, more preferably 0.2 ~ 10 hour.

＜ pulverization process ＞

The manufacture method of the carbon fiber of the present invention can have pulverization process step.Pulverization process preferably removes in thermoplastic resin Implement in step, and/or carbonization calcining step.As breaking method, preferably using jet mill, ball mill, ball mill, impeller The atomizers such as grinding machine, shredding machine, it can be classified as needed after being pulverized.In the case of case of wet attrition, after being pulverized Decentralized medium is removed, now if 2 aggegations significantly occur, then processing thereafter becomes extremely difficult.In this case, It is preferred that carry out size degradation operation using ball mill, jet mill etc. after the drying.

2. nonaqueous secondary battery electrode mixture layer

2nd present invention is that the electrode for nonaqueous electrolyte secondary battery mixture layer formed using above-mentioned fibrous carbon (is had below When be also referred to as " electrode mixture layer ").Fibre of the electrode mixture layer at least containing electrode active material and the invention described above Tie up shape carbon.The different foregoing threadiness of the invention of more than two kinds of such as avarage fiber diameter, average fiber length can be contained Carbon.The electrode mixture layer of the present invention can further contain other carbon series conductive auxiliary agent, bonding agents.

The thickness (thickness) of electrode mixture layer of the present invention is not particularly limited, preferably 50 ~ 5000 μm, more preferably 50~1000μm.If thickness is less than 50 μm, when manufacturing the battery unit of high power capacity, largely using barrier film, collector, electricity The volume occupation rate of electrode active material in pool unit reduces.This is undesirable, purposes from the viewpoint of energy density It is quite limited.When thickness is more than 5000 μm, easily cracked in electrode mixture layer, manufacture is more difficult.It should illustrate, The thickness of electrode mixture layer in the present invention refers to the thickness for not including the only electrode mixture layer of the thickness of aftermentioned collector. As the assay method of the thickness of electrode mixture layer, it is not particularly limited, such as can be measured using micrometer.

The rechargeable nonaqueous electrolytic battery manufactured as the electrode mixture layer using the present invention, can enumerate lithium ion two Primary cell is as representational battery.Hereinafter, the positive active material and negative electrode active for being used in lithium rechargeable battery Material illustrates.

＜ positive active materials ＞

The positive active material included in electrode mixture layer as the present invention, can be used in rechargeable nonaqueous electrolytic battery In known positive active material.For example, if lithium rechargeable battery, then it is suitably for that release lithium ion can be received Containing lithium metal oxide.Contain lithium metal oxide as this, can enumerate comprising lithium and selected from Co, Mg, Mn, Ni, Fe, Al, The composite oxides of at least one kind of element in Mo, V, W and Ti etc..

Specifically, Li can be exemplified_xCoO₂、Li_xNiO₂、Li_xMnO₂、Li_xCo_aNi_1-aO₂、Li_xCo_bV_1-bO_z、 Li_xCo_bFe_1-bO₂、Li_xMn₂O₄、Li_xMn_cCo_2-cO₄、Li_xMn_cNi_2-cO₄、Li_xMn_cV_2-cO₄、Li_xMn_cFe_2-cO₄, (here, x= 0.02 ~ 1.2, a=0.1 ~ 0.9, b=0.8 ~ 0.98, c=1.2 ~ 1.96, z=2.01 ~ 2.3) etc..As preferably containing lithium metal oxidation Thing, Li can be enumerated_xCoO₂、Li_xNiO₂、Li_xMnO₂、Li_xCo_aNi_1-aO₂、Li_xMn₂O₄、Li_xCo_bV_1-bO_z(here, x, a, b and z It is same as described above).It should illustrate, x value is the value before discharge and recharge starts, and is increased and decreased by discharge and recharge.Above-mentioned positive electrode active material Matter may be used singly or in combination of two or more.

The average grain diameter of positive active material is preferably less than 10 μm, more preferably 0.05 ~ 7 μm, is more preferably 1 ~ 7 μm.If average grain diameter is more than 10 μm, the efficiency of the discharge and recharge reaction under high current can reduce sometimes.

The content of positive active material in the electrode mixture layer of the present invention is preferably more than 60 mass %, more preferably 70 ~ 98.5 mass %, more preferably 75 ~ 98.5 mass %.During less than 60 mass %, energy density is dfficult to apply to sometimes It is required that in high power supply purposes.During more than 98.5 mass %, bonding dosage is very few, so as to be produced sometimes in electrode mixture layer Crackle or electrode mixture layer are peeled off from collector.Further, fibrous carbon, the content of carbon series conductive auxiliary agent are very few, so as to Sometimes the electric conductivity of electrode mixture layer becomes insufficient.

＜ negative electrode active materials ＞

The negative electrode active material included in electrode mixture layer as the present invention, can be used in rechargeable nonaqueous electrolytic battery In known negative electrode active material.It is, for example, possible to use as can receive release lithium ion material carbon material, include Si and/or Sn alloy, oxide etc..Among these, from the viewpoints such as cost, preferably carbon material.As above-mentioned carbon materials Material, can enumerate native graphite, by being heat-treated Delanium, Jiang Shu to manufacture to petroleum coke or coal measures coke Hard carbon, mesophase pitch system carbon material etc. obtained from fat carbonization.

During using native graphite, Delanium, from the viewpoint of increase battery capacity, obtained by powder X-ray line diffraction The interplanar distance d (002) in (002) face of graphite-structure be preferably in 0.335 ~ 0.337nm scope.Native graphite refers to conduct The graphite material of ore and natural output.Native graphite can be divided into the high squamous of crystallization degree according to its outward appearance and character This 2 kinds of the graphite amorphous graphite low with crystallization degree.It is foliated flakey stone that flaky graphite, which can be further divided into outward appearance, Ink and block flaky graphite.The place of production of native graphite, character, species are not particularly limited.Furthermore, it is possible to native graphite Or the particle manufactured using native graphite as raw material implements heat treatment to use.

Graphite that Delanium refers to make by extensive artificial means and be similar to graphite perfect cystal graphite Material.For example, it can be manufactured by following manner：It will be obtained by distillation by coal carbonization, crude oil is residue obtained etc. Tar, coke 500 ~ 1000 DEG C or so it is lower calcine after, more than 2000 DEG C at a temperature of graphitization, so as to manufacture.In addition, from It is also one kind in Delanium carbon is separated out the kish obtained from again in molten iron.

As negative electrode active material, in addition to carbon material, if using the alloy for including Si and/or Sn, and with list Body is compared using Si and/or Sn situation, using the situation of respective oxide, and the expansion rate of electrode during discharge and recharge diminishes, Cycle characteristics becomes good.Particularly preferably Si systems alloy.As Si systems alloy, can enumerate selected from B, Mg, Ca, Ti, Fe, Alloy of at least one kind of element and Si in Co, Mo, Cr, V, W, Ni, Mn, Zn and Cu etc. etc..Specifically, can exemplify SiB₄、SiB₆、Mg₂Si、Ni₂Si、TiSi₂、MoSi₂、CoSi₂、NiSi₂、CaSi₂、CrSi₂、Cu₅Si、FeSi₂、MnSi₂、VSi₂、 WSi₂、ZnSi₂Deng.Above-mentioned negative electrode active material may be used singly or in combination of two or more.

The average grain diameter of the negative electrode active material is less than 10 μm.If average grain diameter is more than 10 μm, under high current The efficiency of discharge and recharge reaction can reduce.Average grain diameter is preferably 0.1 ~ 10 μm, more preferably 1 ~ 7 μm.

＜ bonding agents ＞

As the bonding agent that uses in the electrode mixture layer of the present invention, can use can carry out electrode moulding and have to fill The known bonding agent of the electrochemical stability divided.As the bonding agent, polyvinyl alcohol, polypropylene can be exemplified Acid, carboxymethyl cellulose, polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene ribber (SBR), fluorine Olefin copolymer cross-linked polymer, polyimides, polyamidoimide, aromatic polyamides, phenolic resin etc..It is particularly preferably poly- Vinylidene fluoride (PVDF).Above-mentioned bonding agent may be used singly or in combination of two or more.Shape as bonding agent State, it is not particularly limited, can is solid-like, or liquid (such as emulsion).Bonding agent can contemplate the system of electrode Make dissolubility in method (be kneaded especially for dry type or wet type is kneaded), electrolyte etc. and suitably select.

The content of bonding agent in the electrode mixture layer of the present invention is preferably 1 ~ 25 mass %, more preferably 3 ~ 20 matter Measure %, more preferably 5 ~ 20 mass %.During more than 25 mass %, the active matter quality in electrode tails off, the energy of gained battery Density is easily reduced.

Carbon series conductive auxiliary agent ＞s of the ＜ in addition to the fibrous carbon of the present invention

The electrode mixture layer of the present invention can also include the carbon series conductive auxiliary agent in addition to the fibrous carbon of the present invention.As except Carbon series conductive auxiliary agent outside the fibrous carbon of the present invention, for example, carbon black, acetylene black, CNT, VGCF, scale Shape carbon, graphene, graphite.These carbon series conductive auxiliary agents may be used singly or in combination of two or more.

The average grain diameter of these carbon series conductive auxiliary agents is preferably 10 ~ 200nm, more preferably 20 ~ 100nm.

The content of the carbon series conductive auxiliary agent in addition to fibrous carbon in the electrode mixture layer of the present invention is preferably 0.5 ~ 5 Quality %, more preferably 0.5 ~ 4 mass %, more preferably 1 ~ 3 mass %.

3. electrode for nonaqueous electrolyte secondary battery

3rd present invention is to form electrode for nonaqueous electrolyte secondary battery (the also letter sometimes below of above-mentioned electrode mixture layer Referred to as " electrode ").Electrode mixture layer of the electrode formed with the present invention at least one surface of collector.

As the preparation method of the electrode for the electrode mixture layer for possessing the present invention, generally following two methods.It is a kind of Method be by above-mentioned electrode active material, above-mentioned fibrous carbon and bonding agent as needed, other compositions mixed milling simultaneously Film is made by extrusion molding, after being rolled, being stretched, the method that is bonded with collector.

Another method be by above-mentioned electrode active material, above-mentioned fibrous carbon, bonding agent, dissolve bonding agent solvent, Mixed with other compositions so as to prepare slurry, the slurry is coated on collection liquid surface, after removing solvent, the side that is suppressed Method.

In the case of the present invention, either method can be used, but latter method is suitable, is entered below for latter method Row is described in detail.

Solid component concentration in above-mentioned slurry (refers to that the total quality of the composition in addition to the solvents of above-mentioned slurry is being starched Shared ratio in the all-mass of material) it is preferably 10 ~ 30 mass %, more preferably 15 ~ 25 mass %.If solid component concentration More than 30 mass %, then it is difficult to make uniform slurry sometimes.If solid component concentration is less than 10 mass %, the viscosity of slurry Insufficient, the thickness for the electrode mixture layer being laminated on a current collector sometimes becomes uneven.

As the solvent used in slurry, it is not particularly limited, 1-METHYLPYRROLIDONE (NMP), diformazan can be exemplified Yl acetamide (DMAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO).Particularly preferably NMP or DMAc.It is above-mentioned molten Agent may be used singly or in combination of two or more.

When making electrode, if the thixotropy in slurry is too strong, the mobility for being suitable for coating is difficult to ensure that sometimes. In the case of so, slurried auxiliary agent can be used.By adding slurried auxiliary agent, even if can also ensure that with few quantity of solvent Sufficient mobility, also significantly improve the dispersiveness of carbon series conductive auxiliary agent.Additionally it is possible to suppress the crackle after solvent removes Generation.As slurried auxiliary agent, PVP, carboxymethyl cellulose, polyvinyl acetate, poly- can be exemplified Vinyl alcohol.In particular it is preferred to it is PVP.Above-mentioned slurried auxiliary agent can be used alone, and can also combine makes Use two or more.As the addition of slurried auxiliary agent, the total amount relative to the composition in addition to the solvents in slurry is preferably Below 10 mass %, more preferably 0.5 ~ 10 mass %, more preferably 0.5 ~ 8 mass %.If the addition of slurried auxiliary agent More than 10 mass %, then slurry viscosity drastically reduces on the contrary, and generation is scattered bad, so as to be difficult to make suitable slurry sometimes.Slurry When the addition of materialization auxiliary agent is less than 0.5 mass %, it is difficult to show the effect of slurried auxiliary agent.

Above-mentioned slurry is coated on the surface of aftermentioned collector.As coating method, can use known in scraper for coating etc. Coating method.After coating, for example, by the heating that preferably 60 ~ 180 minutes are carried out at 60 ~ 100 DEG C, preferably 75 ~ 85 DEG C Processing, so as to remove solvent.Thereafter, by suppress solvent remove after coating material, can manufacture the present invention electrode.Preferably Pressing conditions is to be carried out 1 ~ 5 minute under 10 ~ 30Pa pressure.

As the collector for forming electrode, arbitrary conductive material can be used.Such as aluminium, nickel, iron, no can be used The metal material of rust steel, titanium or copper.In particular it is preferred to be aluminium, stainless steel or copper, more preferably using aluminium or implement what carbon was coated with Aluminium.

As the thickness of collector, preferably 10 ~ 50 μm.

4. rechargeable nonaqueous electrolytic battery

4th present invention is the rechargeable nonaqueous electrolytic battery for including electrode of the invention and forming.

The rechargeable nonaqueous electrolytic battery of the present invention using electrode of the invention and uses in positive pole and/or negative pole Known barrier film, electrolyte and form.As rechargeable nonaqueous electrolytic battery, lithium rechargeable battery can be exemplified.

The rechargeable nonaqueous electrolytic battery of the present invention is as obtained from being formed on the surface of collector positive-electrode mixture layer Negative pole obtained from positive pole, the dielectric substrate comprising electrolyte and negative electrode mix layer are formed on the surface of collector is formed, It is relative with the negative electrode mix layer of negative pole and in positive-electrode mixture layer and negative electrode mix layer with the positive-electrode mixture layer of the positive pole Between insert dielectric substrate mode be laminated.

The battery unit shape of the rechargeable nonaqueous electrolytic battery of the present invention is not particularly limited, the equal energy under arbitrary shape It is enough to implement.Specifically, the battery unit shape such as coin shape, cylinder type, square can be enumerated.Will be more in addition it is also preferred that being made The Inner Constitution for being laminated to obtain to positive and negative electrode and barrier film.At this point it is possible to use known stacking cascade type, convoluted, folding Return the modes such as cascade type.As the exterior material of the rechargeable nonaqueous electrolytic battery of the present invention, metal can, aluminium lamination pressure can be enumerated Resin film etc..In the rechargeable nonaqueous electrolytic battery of the present invention, the defined fibrous carbon added in electrode mixture layer has There is linear structure and there is high conductivity, therefore easily form conductive path, excellent charge-discharge characteristic can be obtained.Enter one Step, also improves pole strength.

＜ dielectric substrates ＞

As the dielectric substrate for forming rechargeable nonaqueous electrolytic battery, it can use and the electrolyte such as lithium salts are dissolved in nonaqueous solvents Obtained from nonaqueous electrolytic solution.

Electrical conductivity at 25 DEG C of the electrolyte used in the rechargeable nonaqueous electrolytic battery of the present invention is preferably 1 × 10^- ²More than S/cm.

In general, nonaqueous electrolytic solution has the feature that, proof voltage is high compared with the electrolyte of water system, can obtain High-energy-density., can be without restriction using known material as nonaqueous solvents.Specifically, carbonic acid Asia can be enumerated Propyl ester, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxy-ethane, gamma-butyrolacton, γ-penta Lactone, acetonitrile, nitromethane, methoxyacetonitrile, nitroethane, N,N-dimethylformamide, 3- methoxypropionitriles, N- methyl pyrroles Pyrrolidone, N, N'- methylimidazoles alkanone, dimethyl sulfoxide (DMSO), sulfolane, 3- methyl sulfolanes, methyl ethyl carbonate etc..These are non- Aqueous solvent can be used alone, and can also be mixed with two or more.The solvent used in electrolyte is it is important that with suitable When boiling point, fusing point, viscosity and relative dielectric constant, among above-mentioned, be particularly suitable for use with propylene carbonate or gamma-butyrolacton Material as main body.

The electrolyte used in rechargeable nonaqueous electrolytic battery as the present invention, for example, LiClO₄、LiBF₄、 LiPF₆、LiAlCl₄、LiSbF₆、LiSCN、LiCF₃SO₃、LiCF₃CO₂、LiAsF₆, lower aliphatic carboxylic acid's lithium, LiCl, LiBr, LiI, chloroborane lithium, borate family, imidization salt.As borate family, can enumerate it is double (1,2- Benzenediol closes (2-)-O, O') lithium borate, double (2,3- naphthalenes glycol close (2-)-O, O') lithium borates, double (2,2'- biphenyl glycol closes (2-)-O, O') lithium borates, Double (5- fluoro- 2- oleic acid root conjunction -1- benzene sulfonic acids-O, O') lithium borates etc..As imidization salt, double trifluoro methylsulfonyls can be enumerated Imidization lithium ((CF₃SO₂)₂NLi), the fluorine fourth sulfimide lithium (LiN (CF of trifluoro methylsulfonyl nine₃SO₂)(C₄F₉SO₂)), double five fluorine Second sulfimide lithium ((C₂F₅SO₂)₂NLi) etc..As the concentration of electrolyte, preferably 0.5 ~ 2mol/L.Above-mentioned electrolyte It may be used singly or in combination of two or more.For the purpose of improving cyclical stability, efficiency for charge-discharge etc., Ke Yixiang Additive known to addition in electrolyte.

The electrolyte used in lithium rechargeable battery as the present invention, can also compatibly be used with ethyl-methyl miaow Azoles salt is the ionic liquid of representative.Now, it is not necessary to be dissolved in foregoing nonaqueous solvents and use.

＜ barrier films ＞

During using nonaqueous electrolytic solution as described above, in order to prevent negative electrode mix layer from directly being contacted with positive-electrode mixture layer, one As use barrier film.As the shape of barrier film, can compatibly use paper-like (membranaceous), it is porous it is membranaceous etc. known to shape. As the material of barrier film, cellulose, aromatic polyamides, aliphatic polyimide, polyolefin, Teflon (notes can be exemplified Volume trade mark), polyphenylene sulfide.Among these, from the viewpoint of heat resistance and filming, preferably cellulose paper, aromatics polyamides The perforated membrane of amine or aliphatic polyimide.Above-mentioned barrier film may be used singly or in combination of two or more.As The thickness of barrier film, from the viewpoint of short circuit is prevented, preferably 20 ~ 100 μm or so, but in the present invention, can also apply with Conventional barrier film is compared to 5 ~ 20 μm or so fully thin of barrier film.In the case of using thin barrier film, reduce and be derived from The internal resistance of barrier film, therefore export and improve, also improve the energy density of battery unit.

Embodiment

Hereinafter, the present invention is further elaborated with by embodiment, but the present invention is not therefore by any restriction.Embodiment In various measure, analysis carry out by the following method respectively.

(1) shape of fibrous carbon etc. confirms

Using table above formula electron microscope (Jeol Ltd.'s system, model NeoScope JCM-6000), carry out observation and Photograph taking.The avarage fiber diameter of fibrous carbon etc. determines fibre to be randomly choosed from gained electron micrograph at 300 Dimension diameter and the average value for averagely being obtained its whole measurement result (n=300).For average effective fiber length, Similarly calculate.

(2) the X-ray diffraction measure of fibrous carbon etc.

X-ray diffraction measure uses リガ Network company system RINT-2100, according to JIS R7651 methods, measure interplanar distance (d002), crystalline substance Particle size (La, Lc).

(3) assay method of specific insulation

The measure of specific insulation uses the powder resistance system (MCP-PD51) of ダイヤイ Application ス Star Le メ Application Star company systems, Determined under 0.25 ~ 2.50kN load-carrying using the electrode unit of four probe modes.Specific insulation is according to volume resistance It is 0.4g/cm that rate is denoted as packed density with the graph of a relation (Fig. 6) of the change of packed density³When specific insulation value.

(4) shear rate calculates

Shear rate inside head bore because the position in head bore is different and and it is non-constant, but pass through in the case of circular head bore Following formula (2), calculated in the case of rectangle head bore by following formula (3) as apparent shear rate.

(I) situation of circular head bore

[number 2]

。

(II) situation of rectangle head bore

[number 3]

。

(5) tensile deformation speed calculates

Tensile deformation speed inside head bore and the tensile deformation speed outside head bore are simultaneously non-constant, but assume deforming Start to deformation to deform with constant tensile deformation speed in the range of terminating, tensile deformation speed is calculated by following formula (4).

[number 4]

。

[embodiment 1]

The manufacture ＞ of ＜ mesophase pitch

By the softening point for eliminating composition insoluble in quinoline be 80 DEG C coal tar asphalt in the presence of Ni-Mo series catalysts, It is hydrogenated with conditions of pressure 13MPa, 340 DEG C of temperature, obtains hydrogenation of coal tar pitch.By the hydrogenation of coal tar pitch normal Pressure, after being heat-treated at 480 DEG C, decompression removes low boiling point component, obtains thick mesophase pitch.Using filter, by this Thick mesophase pitch is filtered at a temperature of 340 DEG C so as to remove foreign matter, thus obtains refined mesophase pitch.

The manufacture ＞ of ＜ superfine fibre shape carbon (CNF-1)

Using as the straight-chain low density polyethylene (LDPE) of thermoplastic resin (EVOLUE (registration mark) SP1510, (strain) プライ system Port リマー systems, MFR=1g/10 minutes) 84 mass parts and the interphase manufactured by above-mentioned preparation method as thermoplasticity carbon precursor Pitch (middle one after another 90.9%, 303.5 DEG C of softening point) 16 mass parts with parallel dual-screw extruding machine, (make by toshiba machine (strain) " TEM-26SS ", barrel zone temperature is 300 DEG C, under stream of nitrogen gas) melting mixing is so as to preparing mesophase pitch composition.

Then, the mesophase pitch composition using a diameter of 0.2mm, is imported into angle as 60 ° by melt spinning machine Circular head bore is made the resin compounded fiber that fibre diameter is 100 μm and (fabric of island-in-sea type of island component is used as using Mesophase Pitch Fiberss Composite fibre).Head bore temperature is 340 DEG C, and spray volume is 3.8g/ head bore/hour, shear rate 1360s^-1, spray linear velocity Ratio, i.e. draw ratio with hauling speed is 4.The tensile deformation speed inside head bore under the conditions of this is 982s^-1, in head bore Outside deformed region is 10mm under head bore, and tensile deformation speed is 9s^-1。

Resin compounded fiber is maintained under oxidizing gas atmosphere, thus stabilizes mesophase pitch, obtains resin Stable composition chemical fibre is tieed up.

Then, fiber is stabilized from above-mentioned resin compounded, removes thermoplastic resin, thus obtain stabilizing fiber.

Gained is stabilized into fiber to be added in ethanol/ion exchange water mixed solvent (volume ratio=1/1), uses mixer Crush, thus make it scattered.Filtering gained dispersion liquid.

Gained stabilisation fiber is warming up in the case where flow is the nitrogen of 1L/ minutes from room temperature with 5 DEG C/min of condition 1000 DEG C, kept for 30 minutes after reaching 1000 DEG C, so as to be carbonized.Further, under argon gas atmosphere, 3 hours are expended From room temperature to 3000 DEG C, superfine fibre shape carbon is thus made.Gained superfine fibre shape carbon is carried out using dry-type jetting grinding machine Size degradation processing.

The avarage fiber diameter (equivalent to the average length of smallest dimension) of gained superfine fibre shape carbon is 250nm, is not sent out Existing branched structure.Average effective fiber length is 15.1 μm.In addition, between the centre plane in (002) face determined by X-ray diffraction method It is 0.3372nm away from d002, crystal grain length (La110) is 111nm, and the thickness (Lc002) of network plane group is 62nm, is crystallinity High fibrous carbon.Metal containing ratio in superfine fibre shape carbon is 30ppm (iron 10ppm, sodium 20ppm).

Use the above-mentioned mass parts of superfine fibre shape carbon (CNF-1) 2, positive active material (LiFePO₄：Precious Izumi Ltd. System, SLFP-ES01) 91 mass parts, polyvinylidene fluoride (Co., Ltd.'s Network レ Ha systems, W#7200) 7 mass as bonding agent Part, making electrode mixture thickness degree is 114 μm, electrode density 2.56g/cm³Electrode.The volume resistance of the electrode is as low as 83 Ω cm, excellent electric conductivity.In addition, as described as follows, the ratio between integrated value of integrated value/oxidation current of reduction current is 0.9, it is reversible electrochemical reaction.The ratio between IA/IB is 0, and electricity is not shown in 2.5 ~ 4.4V (vs.Li/Li+) potential range Chemical reaction.Charge-discharge characteristic is 65%, is excellent.

＜ cyclic voltammetries ＞

Use the mass parts of superfine fibre shape carbon (CNF-1) 50 as carbon series conductive auxiliary agent, the poly- difluoro second partially as bonding agent Alkene (Co., Ltd.'s Network レ Ha systems, W#7200) 50 mass parts, the 1-METHYLPYRROLIDONE as solvent, make slurry.Will be made After the slurry of work is coated on collector (thickness is 15 μm of aluminium foil), 3h is dried at 120 DEG C, thus makes cyclic voltammetry The model electrode of measure.The thickness for the electrode mixture layer being formed in model electrode is 17 μm.

Foregoing model electrode is used as working electrode, made (hard as the dual electrode cell unit to electrode using lithium metal Coin battery).Electrolyte uses the LiPF by including 1mol/L concentration₆Ethylene carbonate/methyl ethyl carbonate mixed solution (3/7 Volume ratio, キシダ chemical companies system) formed electrolyte.Barrier film uses glass fibre non-woven.

Show that the cyclic voltammetry (CV) that measure obtains in 2.5 ~ 5V (vs.Li/Li+) potential range is bent in Fig. 2 Line.According to the curve, the ratio between the integrated value of integrated value/oxidation current of reduction current is 0.9.That is, it is anti-for reversible electrochemistry Should.In addition, the CV curves that measure obtains in 2.5 ~ 4.4V (vs.Li/Li+) potential range are shown in Fig. 3.According to Fig. 2 And the ratio between Fig. 3, IA/IB are 0.That is, electrochemical reaction is not shown in 2.5 ~ 4.4V (vs.Li/Li+) potential range.

Thereby, it is possible to provide reaction of decomposition, conductive auxiliary agent and electrolyte for being difficult to that electrolyte occurs under high voltages etc. The rechargeable nonaqueous electrolytic battery of side reaction.

＜ charge and discharge electrometric determinations ＞

Using foregoing dual electrode cell unit, filled using charge and discharge device (Big Dipper electrician Co. Ltd. system HJ-1005SD8) Electric discharge measure.As discharge and recharge condition, with 0.1mA/cm²After carrying out constant current charge to 5.0V, with 0.1mA/cm²Enter to 2.5V Row constant current discharge.Measurement result is shown in Fig. 4.As a result, charging capacity is 22.7mAh/g, discharge capacity 14.7mAh/ G, efficiency for charge-discharge 65%, it is good.

[embodiment 2]

The manufacture ＞ of ＜ superfine fibre shape carbon (CNF-2)

Using as the high density polyethylene (HDPE) of thermoplastic resin (Co., Ltd.'s プライ system Port リマー company systems, Ha イゼッ Network ス 5000SR；350℃、600s^-1Under melt viscosity be 14Pas, MFR=0.37g/10 minutes) 90 mass parts, as interphase Mesophase pitch AR-MPH (ガス KCCs of Mitsubishi system) 10 mass parts parallel dual-screw extruding machine (Toshiba of pitch Machinery Co., Ltd. TEM-26SS, barrel zone temperature is 310 DEG C, under stream of nitrogen gas) melting mixing, make mesophase pitch combination Thing.Dispersion diameter of the mesophase pitch in thermoplastic resin is 0.05 ~ 2 μm.In addition, the mesophase pitch composition is existed Kept for 10 minutes at 300 DEG C, but do not observe the aggegation of mesophase pitch, dispersion diameter is 0.05 ~ 2 μm.

Then, the use of slit width is 0.2mm by the mesophase pitch composition, slit length 100mm, import angle be 60 ° of rectangular head hole forming is the plane body of 60 μm of thickness.Head bore temperature is 340 DEG C, and spray volume is 2.4kg/ hours, shearing Speed is 1000s^-1, it is 25 to spray linear velocity and the ratio of hauling speed, i.e. draw ratio, and the distance of ejiction opening to chilling roll is 50mm.The tensile deformation speed inside head bore under the conditions of this is 95s^-1, the tensile deformation speed outside head bore is 208s^-1.Sieve aperture be 1.46mm, line footpath be on 0.35mm wire netting, by the plane body of gained with the weight per unit area of chopped fiber Reach 30g/m²Mode be configured to non-woven fabric-like.

Make to be kept for 3 hours among 215 DEG C of air drier by the fibroplastic non-woven fabrics of the resin compounded, thus make Make to stabilize fibroplastic non-woven fabrics by resin compounded.Then, the non-woven fabrics is put into Gas Replacement Vacuum Furnaces, by stove After nitrogen displacement, 1kPa is decompressed to, is heated by the state, removes thermoplastic resin.Heating condition is with 5 DEG C/min Programming rate be warming up to 500 DEG C after, at the same temperature keep 60 minutes.

The non-woven fabrics that this is eliminated to thermoplastic resin is added in alcohol solvent, is applied 30 minutes by ultrasonator Vibration, thus makes stabilisation fiber disperse in a solvent.Filtering is scattered in the stabilisation fiber in solvent, thus makes and is dispersed with Stabilize the non-woven fabrics of fiber.

By this be dispersed with stabilize fiber non-woven fabrics in Gas Replacement Vacuum Furnaces nitrogen gas circulation under, with 5 DEG C/ Minute is warming up to 1000 DEG C, and carries out at the same temperature 0.5 hour after being heat-treated, and is cooled to room temperature.Further, by the nonwoven Cloth is contained in graphite crucible, and using superhigh temperature stove, (storehouse field skill grinds company system, SCC-U-80/150 types, and soaking portion is 80mm (straight Footpath) × 150mm (height)), it is warming up to 2000 DEG C from room temperature with 10 DEG C/min in a vacuum.After reaching 2000 DEG C, it is made After 0.05MPa (gauge pressure) argon gas (99.999%) atmosphere, 3000 DEG C are warming up to 10 DEG C/min of programming rate, Carry out being heat-treated for 0.5 hour at 3000 DEG C.The electron micrograph of gained superfine fibre shape carbon is shown in Fig. 5.

The fibre diameter of the superfine fibre shape carbon obtained in the above described manner through graphitization processing is 150 ~ 600nm (average fibres Tie up a diameter of 280nm), the ratio between average effective fiber length (L) and avarage fiber diameter (D) (L/D) they are 60, without branch, are The very excellent fibrous carbon of dispersiveness.In addition, according to the result determined by X-ray diffraction method, the crystalline substance of the superfine fibre shape carbon Interplanar distance (d002) is 0.3370nm, and crystal grain length (La) is 336.3nm, and the thickness (Lc) of network plane group is 66.7nm, is knot The high fibrous carbon of crystalline substance.In addition, according to Fig. 6, with 0.4g/cm³Packed density filling when powder volume resistance be 0.14 Ω cm, it is the high fibrous carbon of electric conductivity.

Use the above-mentioned mass parts of superfine fibre shape carbon (CNF-2) 2, positive active material (LiFePO₄：Precious Izumi Ltd. System, S-LFP-ES01) 91 mass parts, polyvinylidene fluoride (Co., Ltd.'s Network レ Ha systems, W#7200) 7 matter as bonding agent Part is measured, the thickness for making electrode mixture layer is 106 μm, the density of electrode mixture layer is 2.56g/cm³Electrode.The electrode Volume resistance it is very small, to 63 Ω cm, excellent electric conductivity.

[embodiment 3]

The manufacture ＞ of ＜ superfine fibre shape carbon (CNF-3)

Make mesophase pitch composition same as Example 2.

Then, the mesophase pitch composition using a diameter of 0.2mm, is imported into angle as 60 ° by melt spinning machine Rounded nose hole forming is the long fibre that fibre diameter is 100 μm.Head bore temperature is 340 DEG C, and spray volume is 3.8g/ head bore/hour, Shear rate is 1360s^-1, it is 4 to spray linear velocity and the ratio of hauling speed, i.e. draw ratio.Under the conditions of this inside head bore Tensile deformation speed be 982s^-1, the deformed region outside head bore is 10mm under head bore, and tensile deformation speed is 9s^-1。

Then, by the precursor fiber make length be about 5cm chopped fiber, sieve aperture be 1.46mm, line footpath 0.35mm Wire netting on, 30g/m is reached with the weight per unit area of chopped fiber²Mode be configured to non-woven fabric-like.Hereinafter, by with reality The operation of the identical method of example 2 is applied, obtains superfine fibre shape carbon.The electron micrograph of gained superfine fibre shape carbon is shown in Fig. 7.

The fibre diameter of the superfine fibre shape carbon obtained in the above described manner through graphitization processing is 150 ~ 700nm (average fibres Tie up a diameter of 280nm), the ratio between average effective fiber length (L) and avarage fiber diameter (D) (L/D) they are 60, without branch, are The very excellent superfine fibre shape carbon of dispersiveness.In addition, with 0.4g/cm³Packed density filling when powder volume resistance be 0.14Ω·cm.According to the result determined by X-ray diffraction method, the interplanar distance of the superfine fibre shape carbon obtained in the above described manner (d002) it is 0.3372nm, crystal grain length (La) is 110.7nm, and the thickness (Lc) of network plane group is 67.5nm.

Use the above-mentioned mass parts of superfine fibre shape carbon (CNF-3) 2, positive active material (LiFePO₄：Precious Izumi Ltd. System, S-LFP-ES01) 91 mass parts, polyvinylidene fluoride (Co., Ltd.'s Network レ Ha systems, W#7200) 7 matter as bonding agent Part is measured, making electrode mixture thickness degree is 106 μm, electrode density 2.56g/cm³Electrode.The volume resistance of the electrode is small To 109 Ω cm, excellent electric conductivity.

[comparative example 1]

Graphitization temperature is 2600 DEG C, in addition, carries out operation same as Example 1, makes superfine fibre shape carbon (CNF- 4).The avarage fiber diameter (equivalent to the average length of smallest dimension) of gained superfine fibre shape carbon is 250nm, does not find branch Structure.Average effective fiber length is 15.1 μm.In addition, the average interplanar distance d002 in (002) face determined by X-ray diffraction method For 0.3380nm, crystal grain length (La110) is 59nm, and the thickness (Lc002) of network plane group is 48nm, is the low fiber of crystallinity Shape carbon.

Use the above-mentioned mass parts of superfine fibre shape carbon (CNF-4) 2, positive active material (LiFePO₄：Precious Izumi Ltd. System, S-LFP-ES01) 91 mass parts, polyvinylidene fluoride (Co., Ltd.'s Network レ Ha systems, W#7200) 7 matter as bonding agent Part is measured, making electrode mixture thickness degree is 115 μm, electrode density 2.51g/cm³Electrode.The volume resistance of the electrode is 135 Ω cm, can not be referred to as electric conductivity height.

＜ cyclic voltammetries ＞

Use the mass parts of superfine fibre shape carbon (CNF-4) 50 as carbon series conductive auxiliary agent, the poly- difluoro second partially as bonding agent Alkene (Co., Ltd.'s Network レ Ha systems, W#7200) 50 mass parts, the 1-METHYLPYRROLIDONE as solvent, make slurry.Will be made After the slurry of work is coated on collector (thickness is 15 μm of aluminium foil), 3h is dried at 120 DEG C, thus makes cyclic voltammetry The model electrode of measure.The thickness for the electrode mixture layer being formed in model electrode is 17 μm.

Former electrodes are used as working electrode, in addition, operation same as Example 1 is carried out, thus makes with lithium Metal is as the dual electrode cell unit to electrode.Show in Fig. 8 and determined in 2.5 ~ 5V (vs.Li/Li+) potential range Obtained CV curves.According to the curve, the integrated value of integrated value/oxidation current of reduction current is 0.84.In addition, show in Fig. 9 The CV curves that measure obtains in 2.5 ~ 4.4V (vs.Li/Li+) potential range are gone out.According to Fig. 8 and Fig. 9, the ratio between IA/IB For 0.That is, electrochemical reaction is not shown in 2.5 ~ 4.4V (vs.Li/Li+) potential range.

＜ charge and discharge electrometric determinations ＞

Using foregoing dual electrode cell unit, charge and discharge electrometric determination same as Example 1 is carried out.Measurement result is shown in Figure 10.Fill Capacitance is 26.8mAh/g, discharge capacity 17.0mAh/g, efficiency for charge-discharge 63%.

[comparative example 2]

The manufacture ＞ of ＜ fibrous carbons (MWCNT)

Catalyst containing Fe and Co is put into quartz tubular reactor, nitrogen displacement will be used in reactor, in circulation nitrogen While gas gas, reactor is expended 60 minutes from room temperature and be warming up to 690 DEG C.It is 690 DEG C to maintain temperature, while nitrogen is cut The mixed gas A of nitrogen and hydrogen is changed to, carries out reduction reaction.After reduction reaction, it is 690 DEG C to maintain temperature, while will mixing Gas A switches to the mixed gas B of hydrogen and ethylene gas, carries out vapor phase growth reaction.Mixed gas B is switched into nitrogen, Nitrogen displacement will be used in reactor, be cooled to room temperature.

The avarage fiber diameter (equivalent to the average length of smallest dimension) of gained fibrous carbon is 150nm, has branch Structure.Average effective fiber length is 8 μm.In addition, the average interplanar distance d002 in (002) face determined by X-ray diffraction method is 0.3383nm, crystal grain length (La110) are 44nm, and the thickness (Lc002) of network plane group is 28nm, is the low threadiness of crystallinity Carbon.Metal containing ratio is 82ppm (iron 43ppm, Si 39ppm).

Use the mass parts of above-mentioned fibrous carbon (MWCNT) 2, positive active material (LiFePO₄：Precious Izumi Ltd.'s system, S- LFP-ES01) 91 mass parts, polyvinylidene fluoride (Co., Ltd.'s Network レ Ha systems, W#7200) 7 mass parts as bonding agent, Making electrode mixture thickness degree is 116 μm, electrode density 2.54g/cm³Electrode.The volume resistance of the electrode is 245 Ω Cm, electric conductivity are low.

＜ cyclic voltammetries ＞

Use the mass parts of fibrous carbon (MWCNT) 50 as carbon series conductive auxiliary agent, the polyvinylidene fluoride (strain as bonding agent Formula commercial firm Network レ Ha systems, W#7200) 50 mass parts, the 1-METHYLPYRROLIDONE as solvent, make slurry.Will be made After slurry is coated on collector (thickness is 15 μm of aluminium foil), 3h is dried at 120 DEG C, thus makes cyclic voltammetry Model electrode.The thickness for the electrode mixture layer being formed in model electrode is 17 μm.

Former electrodes are used as working electrode, in addition, operation same as Example 1 is carried out, thus makes with lithium Metal is as the dual electrode cell unit to electrode.Show in Figure 11 and surveyed in 2.5 ~ 5V (vs.Li/Li+) potential range Surely the CV curves obtained.According to the curve, the integrated value of integrated value/oxidation current of reduction current is 0.81.I.e., using the teaching of the invention it is possible to provide The nonaqueous electrolyte for being difficult to occur the side reactions such as the reaction of the decomposition of electrolyte, conductive auxiliary agent and electrolyte under high voltages is secondary Battery.In addition, the CV curves that measure obtains in 2.5 ~ 4.4V (vs.Li/Li+) potential range are shown in Figure 12.According to The ratio between Figure 11 and Figure 12, IA/IB are 0.044.

＜ charge and discharge electrometric determinations ＞

Using foregoing dual electrode cell unit, charge and discharge electrometric determination same as Example 1 is carried out.Measurement result is shown in Figure 13.Fill Capacitance is 9.1mAh/g, discharge capacity 4.6mAh/g, efficiency for charge-discharge 51%.

[comparative example 3]

Using as the low Spherical Carbon of the crystallinity of carbon series conductive auxiliary agent, (AB, average grain diameter 35nm, this is equivalent to smallest dimension Average length) 2 mass parts, positive active material (LiFePO₄：Precious Izumi Ltd.'s system, S-LFP-ES01) 91 mass parts, make For polyvinylidene fluoride (Co., Ltd.'s Network レ Ha systems, W#7200) 7 mass parts of bonding agent, electrode mixture thickness degree is made For 110 μm, electrode density 2.54g/cm³Electrode.The volume resistance of the electrode is 851 Ω cm, and electric conductivity is low.

＜ cyclic voltammetries ＞

Former electrodes are used as working electrode, in addition, operation same as Example 1 is carried out, thus makes with lithium metal As the dual electrode cell unit to electrode.Show in Figure 14 and determined in 2.5 ~ 5V (vs.Li/Li+) potential range The CV curves arrived.According to the curve, the integrated value of integrated value/oxidation current of reduction current is 0.48.In addition, shown in Figure 15 The CV curves that measure obtains in 2.5 ~ 4.4V (vs.Li/Li+) potential range.According to Figure 14 and Figure 15, the ratio between IA/IB For 0.124.

＜ charge and discharge electrometric determinations ＞

Using foregoing dual electrode cell unit, charge and discharge electrometric determination same as Example 1 is carried out.Measurement result is shown in Figure 16.Fill Capacitance is 5.1mAh/g, discharge capacity 1.7mAh/g, efficiency for charge-discharge 33%.

[embodiment 4]

Then, the mesophase pitch composition is used into wide 0.4mm slit width, slit length 100mm, importing angle Start for 60 °, deformation to the plane body that the rectangular head hole forming that the distance that deformation terminates is 1.7mm is 90 μm of thickness.Head bore Temperature is 340 DEG C, and spray volume is 2.4kg/ hours, shear rate 250s^-1, spray the ratio, i.e. of linear velocity and hauling speed Draw ratio is 40, and the distance (distance that the deformation outside head bore starts to terminate to deformation) of ejiction opening to chilling roll is 50mm.The tensile deformation speed inside head bore under the conditions of this is 23s^-1, the tensile deformation speed outside head bore is 267s^-1.By the plane body of gained sieve aperture be 1.46mm, line footpath be that 30g/m is reached with weight per unit area on 0.35mm wire netting² Mode be configured to non-woven fabric-like.

Make to be kept for 3 hours among 215 DEG C of air drier by the fibroplastic non-woven fabrics of the resin compounded, thus make Make to stabilize fibroplastic non-woven fabrics by resin compounded.Then, the non-woven fabrics is put into Gas Replacement Vacuum Furnaces, by stove After nitrogen displacement, 1kPa is decompressed to, is heated by the state, removes thermoplastic resin.Heating condition is with 5 DEG C/min Programming rate be warming up to 500 DEG C after, at the same temperature keep 60 minutes.Thus, obtain eliminating the nothing of thermoplastic resin Spin the fibrous carbon precursor of cloth-like.The cross-section samples of the fibrous carbon precursor are prepared, implements the electron microscope observation in section, asks Go out avarage fiber diameter.Fibre diameter is 200 ~ 900nm (avarage fiber diameter 400nm, standard deviation 120nm), fiber The standard deviation of diameter divided by the value of avarage fiber diameter are 0.30.Electron micrograph is shown in Figure 17.

Then, the fibrous carbon precursor of the non-woven fabric-like for eliminating thermoplastic resin of above-mentioned making is used into vacuum gas Displacement stove under nitrogen gas circulation, be warming up to 1000 DEG C with 5 DEG C/min, and carry out being heat-treated for 0.5 hour at the same temperature Afterwards, it is cooled to room temperature.Further, the non-woven fabrics is contained in graphite crucible, using superhigh temperature stove (storehouse field skill grinds company system, SCC-U-80/150 types, soaking portion are 80mm (diameter) × 150mm (height)), in a vacuum from room temperature with 10 DEG C/min of heatings To 2000 DEG C.After reaching 2000 DEG C, after argon gas (99.999%) atmosphere of 0.05MPa (gauge pressure) is made, with 10 DEG C/min Programming rate be warming up to 3000 DEG C, carried out at 3000 DEG C 0.5 hour be heat-treated, obtain superfine fibre shape carbon.The superfine fibre The avarage fiber diameter 250nm of shape carbon is tieed up, is the very excellent fibrous carbon of dispersiveness without branch.The superfine fibre shape carbon Interplanar distance (d002) be 0.3370nm, crystal grain length (La) is 111, and the thickness (Lc) of network plane group be 66.7nm, is to tie The high superfine fibre shape carbon of crystalline substance.In addition, the standard deviation of fibre diameter divided by the value (coefficient of variation) of avarage fiber diameter are low In 0.50, fibre diameter it is uneven few.

[embodiment 5]

Using as the high density polyethylene (HDPE) of thermoplastic resin (Co., Ltd.'s プライ system Port リマー company systems, Ha イゼッ Network ス 5000SR；350℃、600s^-1Under melt viscosity be 14Pas, MFR=0.37g/10 minutes) 84 mass parts, as interphase Mesophase pitch AR-MPH (ガス KCCs of Mitsubishi system) 16 mass parts parallel dual-screw extruding machine (Toshiba of pitch Machinery Co., Ltd. TEM-26SS, barrel zone temperature is 310 DEG C, under stream of nitrogen gas) melting mixing, make mesophase pitch combination Thing.Dispersion diameter of the mesophase pitch in thermoplastic resin is 0.05 ~ 2 μm.In addition, the mesophase pitch composition is existed Kept for 10 minutes at 300 DEG C, but do not observe the aggegation of mesophase pitch, dispersion diameter is 0.05 ~ 2 μm.

Then, the mesophase pitch composition is used into wide 0.2mm slit width, slit length 100mm, importing angle Start for 60 °, deformation to the plane body that the rectangular head hole forming that the distance that deformation terminates is 1.7mm is 90 μm of thickness.Head bore Temperature is 340 DEG C, and spray volume is 2.4kg/ hours, shear rate 1000s^-1, spray the ratio, i.e. of linear velocity and hauling speed Draw ratio is 6, and the distance of ejiction opening to chilling roll is 90mm.The tensile deformation speed inside head bore under the conditions of this is 95s^-1, the tensile deformation speed outside head bore is 6s^-1.In addition, processing same as Example 2 is carried out, is obtained superfine Fibrous carbon.The avarage fiber diameter 570nm of the superfine fibre shape carbon, it is the very excellent threadiness of dispersiveness without branch Carbon.In addition, the interplanar distance (d002) of the superfine fibre shape carbon is 0.3368nm, crystal grain length (La) is 113.9nm, network plane The thickness (Lc) of group is 59.1nm, is the high fibrous carbon of crystallinity.

[embodiment 6]

Make mesophase pitch composition same as Example 5.Then, the mesophase pitch composition is used into wide 0.2mm Slit width, slit length 100mm, import angle be 60 °, deformation start the rectangle for being 1.7mm to the distance that deformation terminates Head bore is shaped to the plane body of 100 μm of thickness.Head bore temperature is 340 DEG C, and spray volume is 2.4kg/ hours, and shear rate is 1000s^-1, it is 6 to spray linear velocity and the ratio of hauling speed, i.e. draw ratio, and the distance of ejiction opening to chilling roll is 50mm.Should Under the conditions of the tensile deformation speed inside head bore be 95s^-1, the tensile deformation speed outside head bore is 12s^-1.Except this it Outside, processing same as Example 2 is carried out, obtains superfine fibre shape carbon.The avarage fiber diameter of the superfine fibre shape carbon 360nm, it is the very excellent fibrous carbon of dispersiveness without branch.In addition, the interplanar distance (d002) of the fibrous carbon is 0.3368nm, crystal grain length (La) are 132.1nm, and the thickness (Lc) of network plane group is 52.7nm, is the high threadiness of crystallinity Carbon.

[embodiment 7]

Make mesophase pitch composition same as Example 5.Then, the mesophase pitch composition is used into wide 0.4mm Slit width, slit length 100mm, import angle be 60 °, deformation start the rectangle for being 1.7mm to the distance that deformation terminates Head bore is shaped to the plane body of 140 μm of thickness.Head bore temperature is 340 DEG C, and spray volume is 4.8kg/ hours, and shear rate is 500s^-1, it is 10 to spray linear velocity and the ratio of hauling speed, i.e. draw ratio, and the distance of ejiction opening to chilling roll is 90mm.Should Under the conditions of the tensile deformation speed inside head bore be 46s^-1, the tensile deformation speed outside head bore is 18s^-1.Except this it Outside, processing same as Example 2 is carried out, obtains superfine fibre shape carbon.The avarage fiber diameter of the superfine fibre shape carbon 600nm, it is the very excellent fibrous carbon of dispersiveness without branch.In addition, the interplanar distance (d002) of the superfine fibre shape carbon For 0.3368nm, crystal grain length (La) is 182.3nm, and the thickness (Lc) of network plane group is 61.9nm, is the high fiber of crystallinity Shape carbon.

[embodiment 8]

Make mesophase pitch composition same as Example 5.Then, the mesophase pitch composition is used into wide 0.4mm Slit width, slit length 100mm, import angle be 60 °, deformation start the rectangle for being 1.7mm to the distance that deformation terminates Head bore is shaped to the plane body of 130 μm of thickness.Head bore temperature is 340 DEG C, and spray volume is 4.8kg/ hours, and shear rate is 500s^-1, it is 10 to spray linear velocity and the ratio of hauling speed, i.e. draw ratio, and the distance of ejiction opening to chilling roll is 50mm.Should Under the conditions of the tensile deformation speed inside head bore be 46s^-1, the tensile deformation speed outside head bore is 33s^-1.Except this it Outside, processing same as Example 2 is carried out, obtains superfine fibre shape carbon.The avarage fiber diameter of the superfine fibre shape carbon 420nm, it is the very excellent fibrous carbon of dispersiveness without branch.In addition, the interplanar distance (d002) of the superfine fibre shape carbon For 0.3368nm, crystal grain length (La) is 181.0nm, and the thickness (Lc) of network plane group is 53.2nm, is the high fiber of crystallinity Shape carbon.

[embodiment 9]

Make mesophase pitch composition same as Example 5.Then, the mesophase pitch composition is used into wide 0.8mm Slit width, slit length 100mm, import angle be 60 °, deformation start the rectangle for being 1.7mm to the distance that deformation terminates Head bore is shaped to the plane body of 50 ~ 120 μm of thickness.Head bore temperature is 340 DEG C, and spray volume is 2.4kg/ hours, shear rate For 63s^-1, it is 80 to spray linear velocity and the ratio of hauling speed, i.e. draw ratio, and the distance of ejiction opening to chilling roll is 50mm. The tensile deformation speed inside head bore under the conditions of this is 5s^-1, the tensile deformation speed outside head bore is 533s^-1.Except this Outside, processing same as Example 2 is carried out, obtains superfine fibre shape carbon.The avarage fiber diameter of the superfine fibre shape carbon 390nm, it is the very excellent fibrous carbon of dispersiveness without branch.In addition, the interplanar distance (d002) of the superfine fibre shape carbon For 0.3367nm, crystal grain length (La) is 148.0nm, and the thickness (Lc) of network plane group is 64.3nm, is the high fiber of crystallinity Shape carbon.

[comparative example 4]

Make mesophase pitch composition same as Example 2.Then, the mesophase pitch composition is passed through into melt spinning Machine, the use of a diameter of 0.2mm, importing angle is that 60 ° of rounded nose hole forming is the long fibre that fibre diameter is 160 μm.Head bore temperature Spend for 340 DEG C, spray volume is 4.0g/ head bore/hour, shear rate 1414s^-1, spray linear velocity and hauling speed ratio, I.e. draw ratio is 1.6.The tensile deformation speed inside head bore under the conditions of this is 1021s^-1, the deformed region outside head bore For 10mm under head bore, tensile deformation speed is 2.5s^-1.In addition, processing same as Example 2 is carried out, obtains superfine fibre Tie up shape carbon.The avarage fiber diameter 300nm of the superfine fibre shape carbon, it is the very excellent fibrous carbon of dispersiveness without branch. However, the interplanar distance (d002) of the superfine fibre shape carbon is 0.3373nm, crystal grain length (La) is 90.7nm, network plane group's Thickness (Lc) is 47.6nm, and crystallinity is low.

[table 1]

。

Description of reference numerals

10 head bore

11 deformation starting points

13 deformation end points

15 slit streams

θ imports angle.

Claims

1. fibrous carbon, it is characterised in that average effective fiber length is 1 ~ 100 μm, and the crystal grain determined by X-ray diffraction method is grown It is 100 ~ 500nm to spend (La).

2. fibrous carbon according to claim 1, wherein, the avarage fiber diameter of the fibrous carbon is 100nm ~ 1 μm.

3. fibrous carbon according to claim 1, wherein, the Boron contents of the fibrous carbon are below 1 mass ppm.

4. fibrous carbon according to claim 1, wherein, the fibrous carbon is pitch-based carbon fiber.

5. electrode for nonaqueous electrolyte secondary battery mixture layer, it is included：Electrode active material and include claim 1 institute The carbon series conductive auxiliary agent for the fibrous carbon stated.

6. electrode for nonaqueous electrolyte secondary battery mixture layer according to claim 5, wherein, the nonaqueous electrolyte The thickness of electrode for secondary battery mixture layer is 50 ~ 5000 μm.

7. electrode for nonaqueous electrolyte secondary battery mixture layer according to claim 5, wherein, with comprising described non-aqueous Electrolyte secondary battery is by the use of the electrode of electrode mixture layer as working electrode, using lithium metal as to electrode, using comprising The LiPF of 1mol/L concentration₆Ethylene carbonate/methyl ethyl carbonate mixed solution (volume (25 DEG C) ratio=3/7), in 2.5 ~ 5V (vs.Li/Li+) determined in the range of in obtained cyclic voltammogram (CV), integrated value/oxidation current of reduction current is not shown Integrated value be less than 0.6 electrochemical reaction.

8. electrode for nonaqueous electrolyte secondary battery mixture layer according to claim 5, wherein, the fibrous carbon is Meet the fibrous carbon of following conditions：With comprising being made up of the mass parts of fibrous carbon 50 and the mass parts of polyvinylidene fluoride 50 The electrode of the electrode for nonaqueous electrolyte secondary battery mixture layer of 100 mass parts as working electrode, using lithium metal as pair Electrode, use the LiPF for including 1mol/L concentration₆Ethylene carbonate/methyl ethyl carbonate mixed solution (volume (25 DEG C) ratio=3/ 7) in the cyclic voltammogram (CV) that, measure obtains in 2.5 ~ 4.4V (vs.Li/Li+) potential range, following formula (1) is met

The formulas of IA/IB ＜ 0.02 (1)

Here, IA is that oxidation current reaches when cyclic voltammogram measure is carried out in 2.5 ~ 4.4V (vs.Li/Li+) potential range Maximum among current value during maximum, IB are that circulation volt is carried out in 2.5 ~ 5V (vs.Li/Li+) potential range The current value under 5V when Antu determines.

9. electrode for nonaqueous electrolyte secondary battery, it includes collector and claim 5 institute being laminated on the collector The electrode for nonaqueous electrolyte secondary battery mixture layer stated.

10. rechargeable nonaqueous electrolytic battery, it has the electrode for nonaqueous electrolyte secondary battery described in claim 9.

11. the manufacture method of fibrous carbon, it is the method comprising following step：

(1) fibrosis step, comprising thermoplastic resin and will be 1 ~ 150 mass relative to the mass parts of thermoplastic resin 100 The resin combination of the mesophase pitch of part is molded in the molten state, and the mesophase pitch thus is carried out into fibrosis and obtained To resin compounded fiber；

(2) stabilization step, the resin compounded fiber is stabilized, obtains resin compounded and stabilize fiber,

(3) thermoplastic resin removal step, stabilized from the resin compounded in fiber and remove the thermoplastic resin, so as to To stabilisation fiber；

(4) be carbonized calcining step, and the stabilisation fiber is heated under not active atmosphere so as to be carbonized or graphitization, obtains fibre Tie up shape carbon；

Characterized in that, the tropism control that the fibrosis step has mesophase pitch operates.

12. manufacture method according to claim 11, wherein, the tropism control operation includes applying deformation by shearing Method or apply at least one of method of deformation by stretching.

13. manufacture method according to claim 11, wherein, the method for applying deformation by shearing and described pass through It is respectively 5 ~ 10000s that stretching, which applies the shearing deformation speed in the method for deformation and the speed of deformation based on stretching,^-1。

14. manufacture method according to claim 11, wherein, the method for applying deformation by stretching is in head bore The stretching of downstream side.